Chiral and Achiral Crystal Structures of Au 25 (PET) 18 0 Reveal Effects of Ligand Rotational Isomerization on Optoelectronic Properties
Chiral and Achiral Crystal Structures of Au 25 (PET) 18 0 Reveal Effects of Ligand Rotational Isomerization on Optoelectronic Properties
复制标题
Au 25 (PET) 18 0 的手性和非手性晶体结构揭示配体旋转异构化对光电性能的影响
DOI：
10.1002/chem.202202760
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Ackerson, Christopher J.
中科院分区：
文献类型：
--
作者：
Kuda‐Singappulige, Gowri Udayangani;Window, Phillip S.;Hosier, Christopher A.;Anderson, Ian D.;Aikens, Christine M.;Ackerson, Christopher J.
介绍了Au25(PET)18的4种配体旋转异构体的晶体结构。揭示了两个新的配体旋转异构体，并且还提出了两个更高质量的结构（允许完全溶解配体外壳）先前解决的Au25(PET)18簇。其中一个结构缺少反转中心，使其成为第一个解决的手性Au25(SR)18结构。这些结构与先前发表的Au25(SR)18结构相结合，可以分析Au25(SR)18簇的经验配体构象景观。这一分析表明，PET配体内的二面角局限于某些可观察值，而且二面角值是相互依赖的，以一种让人联想到生物分子的二面角，如蛋白质和DNA中的二面角。计算了配体构象异构对光学和电子性质的影响，揭示了配体构象影响纳米簇吸收光谱，这可能为低温下区分异构体提供了一种方法。
The crystal structures of 4 ligand‐rotational isomers of Au25(PET)18are presented. Two new ligand‐rotational isomers are revealed, and two higher‐quality structures (allowing complete solution of the ligand shell) of previously solved Au25(PET)18clusters are also presented. One of the structures lacks an inversion center, making it the first chiral Au25(SR)18structure solved. These structures combined with previously published Au25(SR)18structures enable an analysis of the empirical ligand conformation landscape for Au25(SR)18clusters. This analysis shows that the dihedral angles within the PET ligand are restricted to certain observable values, and also that the dihedral angle values are interdependent, in a manner reminiscent of biomolecule dihedral angles such as those in proteins and DNA. The influence of ligand conformational isomerism on optical and electronic properties was calculated, revealing that the ligand conformations affect the nanocluster absorption spectrum, which potentially provides a way to distinguish between isomers at low temperature.